Process for distillation



Apri! 14,1942 v, ac. SMITH UAL 2,279,764

PROCESS FOR DISTILLATION Filed July 6, 1939 2 Sheets-Sheet l lia-@lgime/whew Eidnajj Ru 55E-11T Van N255 SMQ; iwf@ om April 14, 1942. s. C. SMITH ErAl.

PROCESS `oR DISTILLATION Filed July 6, 1939 2, Sheets-Sheet 2 Lzguz'd apar: Sich-leg E.. E11-nih Ru SEEN T.' Val-LNEES 'wa/'Z 20% am 'ter to the reactionzone,

Patented Apr. 14,' 1942 Sidney C. Smith, Philadelphia, Pa.,

T. Van Ness, Wilmington, Del., E. I. du Pont de Nemours & Company,

and Russell assignors to Wilmington, Del., a corporation of Delaware Application July 6, 1939, Serial No. 283,084

(Cl. 26o-22) 2 Claims.

lThis invention relates to synthetic 'resins and Amore particularly to a new method and equipment for` manufacturing alkyd resins by the solution method.`

The present invention is an improvement over 'the processes described in Patents 2,057,765 and 2,057,766 forthe manufacture of resins of the alkyd or polyhydric alcohol-polybasic acid typel by the solution method.

The term polyhydric resin as used herein means the resinous condensation product resulting from the interaction of one or more polyhydrlc alcohols and one or more organic polynesie-acids, with or without one or more modifying ingredients, such as the following: drying oils, semi-drying oils, non-drying oils, monohydric alcohols, monobasicA or di-basic acids, especially those derived from drying oils, semi-drying oils, and non-drying oils, natural resins and other synthetic resins. The term solution method as used herein indicates a method which comprises heating the reacting ingredients in the presence of a substantially nonreactive solvent, removing the solvent and water of reaction' by distillation and condensation, separating the water from the solvent while both are in the liquid phase, and returning the latsaid process being carried out at sufliciently high temperatures to cause resinication, and suicient to cause gelation.

The solution method for manufacturing resins in the` above mentioned patents is not, without the further features which characterize the present invention, adapted for the production o'f the resins in commercial quantities. The volatilization of the phthalic anhydride and resultant loss of this material through thel Water separator limited the temperature to a maximum. of about 210 C. and required the use lof solvents boiling not substantially above this temperature. By that process it is dicult to make resins of acid numbers as low as 0.5 to 6.0. Also the direct heating of the reaction vessel limits the effective heat transfer to that of the kettle walls in contact with the batch. The reaction time required was from l2' to 36 hours due to the' low reaction temperature, high dilution of the reactants by solvent and the limited surface exposedto thevapor space for the release of solvent and water vapors.

This invention has as an object an improved alcohol-pclybasic acid for a period of time lny ber;

pared to previous methods results in greater resin yields, lower operating cost and the production of lower acid number resins. A further object resides in equipment for accomplishing these results. Other objects will appear hereinafter.

The preferred embodiment of our inventionl is described in connection with the accompanying drawings in which:

Fig.V 1 is an elevation of a. complete apparatus for carrying out our invention;

Fig. 2 is a sectional view of the vapor scrub- Fig. 3 is an elevation partly in section of a portion of the apparatus shown in Fig. 1;

Fig. 4 is a view showing ther view of theapparatus shown in Fig. 1; and

Fig. 5 is a sectional view of another form of scrubber.

The numeral l indicates an insulated reaction vessel or flash tank the bottom of which opens into a conduit leading to the pump 2 which forces the reaction mixture through a tubular heat exchanger 3 after which it is forced into the tank again through a flared end pipe or nozzle t which provides a slit opening. The heat exchanger is of conventional type comprising a method for making alkyd resins by the solution method. A. further object is a solution method for ufacturing alkyd resins which 'as comshell within which the reaction mixture passes through a plurality of thin pipes surrounded by the vapors of a heat transfer material consist- `ing of an eutectic mixture of diphenyl and diphenyl oxide, or by other heating fluid circulating through the heat exchanger from an inlet 30 to outlet 3l. A conduit 5 conducts the vapors from the ash tank through a scrubber 6 to a water cooled condenser l. The scrubber, which is designed to cool and scrub the vapors ascending from the hash tank by the condensed solvent returning from the condenser, is shown in Fig. 2. The scrubber is provided with a. bubble distillation plate St, a solvent entrance pipe l I, exit pipe 6l and plate drain 62'.

Thesolvent returned through pipe il builds up on the plate t0 to the top of the Weir 63'over which it ows to the exit'pipe 6l. The solvent, water, phthalic anhydride and other vapors ascending through the chimney t are' deected by the cup S5 and bubble through the layer of liquid solvent which condenses the volatile ingredients and returns them to the flash tank. The vapors of solvent and water pass up through the line 5 after being reduced in the scrubber from the batch temperature of 220 C. or higher to about C. when a low boiling solvent such as in more detail a furtoluol is used and to about 165 C. when a high boiling 'solvent such as mineral spirits is used.

:The vapors pass through the line 5 to the condenser I and the condensate runsto the cyclone separator 8 where the entrained inert gases are .removed through the pipe 80. lIn the gravity separator 9 the water of reaction which settles to the bottom of these parts is removed through .the valved pipe 90 and the solvent passes from the line 9i through a meter I 0 where the rate of solvent reiluxing is measured by "a weir |01. and then throughk the solventv entrance pipe 'Il into the scrubber. The return pipe Il and plate drain 62 are connected through valves to a line I2 which connects with the solvent exit pipe Bl4 which leads back to the tank. l

The method of conducting the present process in the manufacture of a typical alkyd resin is as follows:

Linseed oil and suiilcient glycerine to form a monoglyceride are charged into the iiash tank. Thel circulating pump is started, Dowtherm vapors at one to three atmospheres pressure admitted to the heater, and thebatch heated to 22.5 C. At a temperature of 93 C..a small amount of iitharge catalyst is added. The oil :and glycerine are held at the reaction tempera- V ture of 225 C. untill a sample indicates `complete mis'cibility of 'one part -of monoglyc'eride in three parts of 95% methyl alcohol. During this stage in the final thin-down of the batch is used as theA Vreiiluxing agent* An amount equal to about 8% of the resin batch .'(excluding thinners) is used ing water to the condenser is used to remove asV much heat as possible from the batch. 'Ihe temperatureV of the thinned batch is about 165 C.

The above description relates to a single-kettle unit. The monozlyceride may be made in a separate kettle. In this case the phthalic anhydride is charged into the monoglyceride, these 'ingredients then charged in the flash tank, reflux solvent added and the process continued asin the single kettle unit.

The solvent concentrations are preferably 2% to 14% and the temperature-from-225" C. to 260 C.

Other and more simplified arrangements may be provided between the condenser and scrubber for separation of the water of reaction and return of solvent to the scrubber. The scrubber may be any of the known types in which the vapors are scrubbed by the solvent. The scrubber may be ofthe sieve plate type or it may provide other types of hailing instead ofthe bubble cap plate. Fig. 5shows a form in which the condensed solvent returning through pipe Ii nows downward around the baiiles 50 and into lthe reaction tank against the upward ilow of Aascending vapors. I

'I'he above process is applicable not only for the production of the resin from the reactants but also for vbeneficial treatment of the resin formed. The process may be used as a further or after treatment of alkyd resins made by the present solution method or by other methods to remove water or cloudiness or to improve the drying properties of the resin.- The present process is applicable to the manufacture of all types of oil modified alkyd resins which are thinned in solvents inert to the resin. Y

The apparatus described above is also useful in dehydrating castor oil, the manufacture of urea-formaldehyde monohydric alcohol resins.

varnishes by the solution method, plasticizers and the reflux rate'such as to provide about four tum-overs of this solvent per hour.

batch brought to reaction temperature of 220 C. One-half hour after the phthalic anhydride ad- .'dition, the remaining glycerine Ain the resin for- `mula is added. 'Ihe batch is held at reaction temperature, maintaining solvent reiluxing, and

samples taken for tests of acid number and viscosity until the desired endpoint is reached.

`Before each sampling, the reaction water is drained downin the separator to the level existing' at thestart to insure the same yproportion ofv Phthalic anhydride is charged into the a'sh tank and the such as castor oil phthalate and dibutyl phthalate, and in fact the present apparatus and process is applicable to any process involving the esteriilcation of two or more ingredients in which a liquid water carrier can be used.

This invention presents several valuable advantages over the previous practice in resin manufacture. Since by reason of the external milligrams of potassium l hydroxide required to neutralize the free acid in one gramof the resin.

When acid number and viscosity Atests indicate that the specifications have been obtained the scrubber by-pass valve isopened, the heat control valve on the heat exchanger closed, and the proper amount of thinners charged into the dash tank. During the thin-down the full'ilo'w of cool- 75 `heat 'exchanger the heat transfer is not limited tothe kettle walls, it is possible to reduce the time required to bring the batch to reaction temperature by as much as 50%. The 'forcing oi the resin or resin reaction mixture` through the small heating tubes of the heat exchanger 'assures uniform heating and eliminates the possibilityof. localized overheating. The nozzle through which the resin or reaction mixture is returned to the iiash tank causes the resin or reaction mixture to pass through the vapor space in thin sheetsabove the mass of material treated inthe tank, or causes the injected material to be broken up in small sheets thereby exposing a large surface for the release'of solvent and water vapors. This' feature of our invention results in a markedly reduced reaction time. For instance, in the case of coconut oil modified resins the -use of the nozzle reduces the reaction time by as muchas 50%. Higher reaction temperatures (up to 260T C.) higher boiling solvents and to 40% required in the prior practice to avoid loss of phthalic anhydride and other ingredients to the condensing system.

The higher reaction temperatures and lower solvent concentrations made possible by this invention both tend toward faster reaction and consequently shorter cooking. Higher acid number resins previously made in l2to 36 hours can bel made in three to iive hours by the method described herein. Lower acid number resins which could not be made by the former equipment and process can be made in 6 to 12 hours bythe procedure of thisinvention.

As many apparentlywidely diierent embodiments of this' invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the specic embodiments thereof except as dened in the appended claims.

We claim: v

l. A process for making resins which comprises placing in a flash tank a solvent composed of a volatile organic liquid water-immiscible Water carrier and a reaction'mixture obtained from rethe ash tank and then into vapor space of the flash tank above the reaction mixture in a stream actants comprising polyhydric alcohol and Ipolycarboxylic acid, forcing the liquid contents from.

its passage therein in said stream, condensing the evolved vapors,"separating the water from the condensate, returning the condensed solvent to the ash tank, and scrubbing the vapors evolved from the ash tank by passing them to the condenser in contact with andcounter-current to the condensed solvent flowing from the condenser to the flash tank.

2. A process for making resins which comprises placing in a flash tank a solventI composed of a volatile organic liquid water-immiscible water carrier, a glyceride less than the triglyceride of 'a monobasic acid,v and phthalic anhydride, forcing the liquid contents from the flash tank and then into the vapor space of the ashtank above the reaction mixture in a stream providing a large surface area, heating said liquid contents exteriorly of the ash tank before its passage therein in said stream, condensing the evolved vapors, separating the water from the condensate, returning the condensed solvent to the ilash tank, and scrubbing the vapors evolved from the flash tank by passing them to the condenser in contact with and countercurrent to the condensed solvent iiowing4 from the condenser to the flash tank.

SIDNEY C. SMITH. RUSSELL T. VAN .NESS. 

